US11453769B2 - Modification of virgin and/or recycled construction polymers, using poly vinyl butyral (PVB), or recycled PVB from industrial waste streams and an alloying copolymer - Google Patents

Modification of virgin and/or recycled construction polymers, using poly vinyl butyral (PVB), or recycled PVB from industrial waste streams and an alloying copolymer Download PDF

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US11453769B2
US11453769B2 US16/980,067 US201916980067A US11453769B2 US 11453769 B2 US11453769 B2 US 11453769B2 US 201916980067 A US201916980067 A US 201916980067A US 11453769 B2 US11453769 B2 US 11453769B2
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Jens Holmegaard
Frank Mundt
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SHARK SOLUTIONS APS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/66—Substances characterised by their function in the composition
    • C08L2666/68—Plasticizers; Solvents

Definitions

  • the following relates to a plasticizer composition for construction polymer compositions.
  • the following relates to a method for modifying a construction polymeric composition.
  • PVC and other construction polymers are used frequently in the construction of various products.
  • the PVC (or other construction polymers) needs a plasticizer to soften or render the polymer matrix more flexible in order to provide the desired physical properties of a certain product.
  • Plasticizers for PVC construction polymers contain phthalates, and/or halogenated compounds. These compounds do however tend to migrate in the PVC matrix and are susceptible to leaching out of the polymer matrix over time, especially when the product is in contact with water. This results in slowly changing physical properties of the product, e.g. by increased brittleness of the product.
  • plasticizers are toxic to humans and/or to the environment. Some of these plasticizers for PVC are gradually phased out.
  • PVC waste is also problematic, because it forms dioxins and/or hydrochloric acid when incinerated. Thus the PVC waste is not easily disposed of. This has also limited the use of PVC.
  • PVC with these modern plasticizers is mostly limited to use as roofing, geomembranes or similar applications.
  • plasticizer solutions for construction polymers in particular for PVC, which are non-migrating in the polymer matrix, and which are non-toxic and with a “green”/environmentally friendly profile.
  • plasticizer solutions for construction polymers in particular for PVC, which are free from halogens, and/or phthalates.
  • plasticizer solutions for construction polymers in particular for PVC, which provide compounded polymer alloys where the plasticizers are non-migrating and thus not leached from the polymer matrix.
  • An aspect relates to a solution for applying plasticizer compositions to construction polymers, e.g. PVC, polyethylenes (PE), polypropylenes (PP), acryl butadiene styrenes (ABS) and/or polyurethanes (PU), where the components of the plasticizer composition are non-migrating in the polymer matrix and thus not easily leached out of the polymer matrix.
  • PVC polyethylenes
  • PP polypropylenes
  • ABS acryl butadiene styrenes
  • PU polyurethanes
  • plasticizer compositions to construction polymers, which are free from halogens, and/or phthalates and/or which are non-toxic and with a “green”/environmentally friendly profile.
  • plasticizer compositions to construction polymers, in particular for PVC, which provide compounded polymer alloys from which plasticizers are non-migrating and thus not leached from the polymer matrix.
  • plasticizer composition for a construction polymer wherein said plasticizer composition comprises 35-65% (by weight) of polyvinylbutyral (PVB) and 65-35% (by weight) of one or more alloying copolymers.
  • This composition is primarily intended as a totally non-migrating plasticizer for flexible construction polymer applications, in particular PVC applications and/or for modification of other polymers as mentioned further below.
  • Composites and construction polymers can also benefit from this polymer-alloy with both elastic and acoustical properties.
  • this balanced weight ratio leads to an extrudable polymer material which can be pelletized and is thus very easy to handle.
  • the plasticizer composition can thus be used as part of a construction polymer blend as described further below.
  • the plasticizer composition is solid and can alternatively be used by directly mixing the individual components of PVB and the alloying copolymer(s) into the construction polymer or polymers as also described further below.
  • This plasticizer composition has surprisingly proven to be superior when PVB is used in combination with the alloying copolymer, and provide unforeseen synergistic effects when applied as a plasticizer composition in construction polymers such as poly vinyl chloride (PVC), in particular recycled PVC, and other virgin or recycled construction polymers, such as polyethylene (PE), polypropylenes (PP), acryl butadiene styrene (ABS) and/or polyurethanes (PU).
  • PVC poly vinyl chloride
  • PE polypropylenes
  • ABS acryl butadiene styrene
  • PU polyurethanes
  • Construction polymers modified with the plasticizer composition according to embodiments of the present invention including modified PVC, form uniform, extrudable and mouldable polymer alloys with changes in mechanical properties, and plasticization where migration of PVB and the alloying copolymer(s) are sterically hindered.
  • the resulting polymer matrix contains a blend of the applied polymers in which the different polymer molecules, i.e. the construction polymer, PVB and the alloying copolymer are intermixed and thus not susceptible to migration within the polymer matrix.
  • the microstructure of the resulting polymer matrix appears more like a true alloy (as known from metals), where the compounds form a “true” all homogeneous mixture, especially in PVC applications.
  • the plasticized polymer matrix often comprises embedded macroscopic or microscopic volumes of isolated plasticizer resulting in a microstructure resembling an emulsion.
  • the plasticizer may be susceptible to migration and/or less efficient plasticizing effect resulting in increased brittleness and/or that the products become brittle much faster, e.g. when exposed to weathering effects.
  • Embodiments of the present invention focus on using poly vinyl butyral (PVB), or recycled PVB from industrial waste streams, as non-migrating plasticizer and impact modifier in a specific and unforeseen combination with alloying polymers.
  • PVB poly vinyl butyral
  • PVB is used as sole plasticizer additive in e.g. PVC
  • a less successful microstructure (with microvolumes of PVB embedded in the construction polymer/PVC matrix) may also result in unwanted drawbacks such as reduced tear strength, risk of partial deterioration over time and risk of uneven freeze-fracture.
  • PVB in a solid state non-migrating plasticizer
  • the above mentioned drawbacks of using PVB as plasticizer, especially in PVC are avoided.
  • PVB can be maximized and the properties of the final polymer matrix enhanced.
  • elongation at break, the change of flexural and tensile modulus, the improved Charpy strength and the maintained surface tension are the most important.
  • embodiments of the present invention give new design possibilities for constructional polymers and in particular PVC, since plasticization is scalable, and the microstructure of the blend reproducible and homogeneous.
  • plasticizer composition according to embodiments of the present invention modifies recycled PVC as well, giving possibility to scale and tune properties of rPVC (recycled or reclaimed PVC) for extended and meaningful reuse. It is in practice possible to extract unwanted plasticizers from the PVC by liquid or supercritical CO 2 extraction, hereby giving possibility of recovering PVC without the problematic previously used plasticizers. Thus, with embodiments of the present invention it is also possible to reuse reclaimed PVC (rPVC) by combining the rPVC with a controlled macromolecular plasticizer according to embodiments of the present invention, by using the plasticizer composition of PVB together with the alloying copolymer.
  • rPVC reclaimed PVC
  • the confined formulation window ascertains the formation of the microstructures of the blend giving the desired modification of the product's physical properties as elongation at break, the change of flexural and tensile modulus, the improved Charpy strength without lowering the surface tension of the compound.
  • Recycled PVB polyvinylbutyral
  • the PVB fraction is reclaimed and thoroughly cleaned, sorted and reprocessed to the highest standards.
  • Pellets are formed of the (reclaimed) PVB where PVB is carefully compounded and extruded to form the pellets.
  • rPVB recycled PVB
  • a “green” or an environmentally friendly profile can be obtained on the new products, because problematic waste streams, that else would be thrown at landfills or incinerated are utilized for new products.
  • the environmental advantage, of the recovered PVB mined from the direct waste stream to incineration or landfill is thus evident.
  • the “green” and environmentally friendly profile is improved even further if the constructional polymers, e.g. PVC, is also recycled from a waste stream.
  • the alloying copolymer(s), see further below, are solids at room temperature and pellets thereof may be mixed with the PVB prior to forming the plasticizer composition pellets in extruders or roll mixers. This simplifies the addition of the plasticizer composition and improves intermixing of the plasticizer composition into the construction polymer stream, especially when it is to be mixed directly into the extruder.
  • the alloying copolymer(s) are provided as separate pellets that are mixed with PVB pellets in the ratios described above or below. This simplifies the production of the plasticizer composition and reduces production costs while not reducing the synergistic effects of PVB and the alloying copolymer(s).
  • the polyvinylbutyral component may be recycled polyvinylbutyral, virgin polyvinylbutyral or a mixture thereof.
  • virgin grades of PVB may be used for this purpose.
  • the alloying polymer may be an Ethylene vinyl alcohol Copolymer Resins (e.g. marketed under the tradename Elvaloy® by Dupont), optionally combined with one or more other alloying copolymer(s) as the synergistic effects on plasticizing effect, as well as the alloying effect on the resulting polymer blend or mixture is particularly pronounced when used together with PVB.
  • the molecular weight of the PVB or rPVB may be in the full range from 25 kg/mol to 465 kg/mol covering both virgin PVB and the experienced variation in rPVB.
  • the plasticizer composition may comprise 40-60% of PVB with 60-40% by weight of the alloying copolymer(s) or 45-55% by weight of PVB and 55-45% by weight of the alloying copolymer(s) or 50% by weight of PVB and 50% by weight of the alloying copolymer(s).
  • the polyvinylbutyral modified with the alloying copolymer may be used in the above mentioned stochiometric ratios to Ethylene vinyl alcohol Copolymer Resins and others. Due to the alloying effect of different polymer groups, hydroxyl- and other polar groups like —Cl in PVC the resulting properties are not linear-combinations of known properties for the pure components, as also the inner microscopical structure are not just a blend of ordinary polymers since the boundaries between domains are not sharp, and the individual polymers not locally recognizable.
  • a polymer composition or blend which comprising a construction polymer and a plasticizer composition as described above, wherein the construction polymer constitutes 25-90% by weight of the polymer blend and the plasticizer composition constitutes 10-75% by weight of the polymer blend composition.
  • the resulting polymer blend compound is primarily intended as a totally non-migrating plasticizer for flexible PVC applications and for impact modification of other polymers.
  • Composites and construction polymers can also benefit from this polymer-alloy with both elastic and acoustical properties.
  • the construction polymer of the polymer composition may be selected from the group comprising polyvinyl chloride (PVC), polypropylene (PP), poly urethane (PU), acryl butadiene styrene (ABS) or polyethylene (PE) and/or mixtures thereof, because the synergistic effect of the plasticizer composition of PVB with the alloying copolymer is most pronounced with these construction polymers.
  • PVC polyvinyl chloride
  • PP polypropylene
  • PU poly urethane
  • ABS acryl butadiene styrene
  • PE polyethylene
  • the plasticizer composition may constitute at least 30% by weight of the amount of the polymeric composition, or 30-50% by weight of the polymer blend composition or 40% of the polymer blend composition. This is because the favourable “alloyed” microstructure of the polymer matrix is most pronounced, and because the synergistic effects of PVB and the alloying copolymer is most pronounced as already discussed above in relation to the plasticizer composition.
  • thermoplastic mixing in extruders or roll mixing can be used to scale the fineness of the blend, where the most intensive and smallest domain size of the resulting blend may be preferred.
  • the polymer composition may comprise a construction polymer, which may be selected from virgin polyvinyl chloride (PVC) or recycled polyvinylchloride (PVC) or a mixture thereof.
  • a construction polymer which may be selected from virgin polyvinyl chloride (PVC) or recycled polyvinylchloride (PVC) or a mixture thereof.
  • the polymer composition may be mixed with one or more further components, such as colorants, stabilizers, antioxidants, fillers, UV filters and/or mixtures thereof.
  • additives such as colorants, preservatives, stabilizers, fillers, UV filters and/or or antioxidants may be added to the polymer blend.
  • One or more suitable additives may be added in an amount of 0.01-65% by weight relative to the total of the final polymer composition after mixing with additives.
  • Suitable stabilizers for plasticized PVC based polymer blends are e.g. Calcium-Zinc complexes, stabilisers based on erythritols, e.g. pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate) (marketed as IrganoxTM 1010), phosphites, such as Tris(2,4-ditert-butylphenyl)phosphite (marketed as IrgafosTM 168), and/or mixtures thereof.
  • Stabilizers may in particular be used in amounts of 0.5-1% by weight of the final composition.
  • stabilizers are used when processing the polymer composition under elevated temperatures. If processing the polymer composition at temperatures above 160° C., there is a risk of degradation of PVB in the polymer composition mixture, which can be avoided by adding stabilizers as mentioned above.
  • Suitable colorants are among others Titanium (IV)-oxide, carbon black, and/or typical well-known colorants used in polymers. Such well-known colorants are usually called masterbatch and ultrabatch compounded colorants containing the colorant and a carrying polymer.
  • fillers such as calciumcarbonate, fibers can be added to the polymer blend in relatively large amounts.
  • inorganic fillers may be added in up to 50% by weight or sometimes up to 60% by weight of the final composition.
  • foaming agents e.g. Hydrocerol® (made by Clairant) can be used in the final polymer composition.
  • foaming agents may be used in amounts of up to 5% by weight of the final composition.
  • the plasticizer composition according to embodiments of the present invention may be solid and may be pelletized to allow fast and effective mixing with the construction polymers.
  • the pelletized plasticiser composition may e.g. be mixed e.g. be mixed with construction polymer raw material (which are typically also pelletized) prior to heating. The mixing can be easily done before the extruder or a two-roll mixer. In some situations, pelletized PVB and pelletized alloying polymer are added separately to the construction polymer in above mentioned amounts of each component.
  • the pelletized plasticizer composition may be added into a flow of melted construction polymer, e.g. by introducing the pellets into a flow mixer which mixes the pellets into the melt and ensures efficient mixing of the plasticizer composition into the construction polymer melt or by mixing the pellets into the melt in the extruder, e.g. at the inlet thereof.
  • the plasticizer pellets will melt and the plasticizer composition will be thoroughly mixed into the construction polymer melt.
  • This thorough mixing of the pelletized plasticizer into the construction polymer also ensures effective dispersion of the plasticizer so as to provide the above-mentioned alloying properties.
  • the method of modifying a construction polymer may comprise that the heating step is included in the shaping step. This often occurs, e.g. when extruding items, where the heating causes melting immediately prior to or while shaping the product into the final shape.
  • the method may include that the plasticizer composition comprises 35-65% (by weight) of polyvinylbutyral (PVB) and 65-35% (by weight) of an alloying copolymer.
  • PVB polyvinylbutyral
  • the method may include that the polymer composition blend comprises 35-45% by weight of the plasticizer composition and 65-55% by weight of construction polymer, or 40% by weight of plasticizer composition and 60% by weight of the construction polymer.
  • the method may include adding one or more additional additives to the mixture of solids of plasticizer composition and construction polymer and to construction polymer blend composition when the polymer blend composition is in solid or melted state.
  • FIG. 1 depicts average values of flexural modulus for a pure PVC reference specimen and test specimens
  • FIG. 2 depicts values of tensile modulus for the pure PVC reference specimen and the test specimens
  • FIG. 3 depicts measured hardness for the pure PVC reference specimen and the test specimens
  • FIG. 4 depicts measurements of elongation at break for the pure PVC reference specimen and a test specimen
  • FIG. 5 depicts measured tensile strength for the pure PVC reference specimen and a test specimen
  • FIG. 6 depicts values of flexural modulus for the pure PVC reference specimen and three test specimens
  • FIG. 7 depicts values of tensile modulus for the pure PVC reference specimen and the three test specimens of FIG. 6 ;
  • FIG. 8 depicts values of Shore D hardness for the pure PVC reference specimen and the three test specimens of FIGS. 6 and 7 ;
  • FIG. 9 depicts values of elongation at break for the pure PVC reference specimen and the three test specimens of FIGS. 6-8 ;
  • FIG. 10 depicts values of tensile strength for the pure PVC reference specimen and the three test specimens of FIGS. 6-9 ;
  • FIG. 11 depicts values of Charpy strength for the pure PVC reference specimen and the three test specimens of FIGS. 6-10 ;
  • FIG. 12 depicts values of tensile modulus for the pure PVC reference specimen and three further test samples
  • FIG. 13 depicts values of Shore D hardness for the pure PVC reference specimen and the three further test samples of FIG. 12 ;
  • FIG. 14 depicts values of elongation at break for the pure PVC reference specimen and the three further test samples of FIGS. 12-13 ;
  • FIG. 15 depicts values of Charpy strength for the pure PVC reference specimen and the three further test samples of FIGS. 12-14 ;
  • FIG. 16 depicts values of contact angle for the pure PVC reference specimen and two test specimens.
  • FIG. 17 depicts values of contact angle for the pure PVC reference specimen and five additional test specimens.
  • PVC and recycled PVC construction polymers as polypropylene (PP), poly urethane (PU), acryl butadiene styrene (ABS) or polyethylene (PE), can be advantageously modified by use of a pelletized blend of PVB and ElvaloyTM within confined limits.
  • the basis-polymer/PVB/blend with the alloying component chosen from ElvaloyTM, EntiraTM, FusabondTM and/or RetainTM polymers or copolymers forms uniform, extrudable and moldable polymer alloys with changes in mechanical properties, and a resulting plasticization sterically hindered in migration.
  • the method may be limited to the following window of formulation for the constituents PVB and alloying copolymer:
  • PVB 35-65% by weight mixed with
  • Alloying copolymer 65-35% by weight
  • a formulation may comprise 45-55% by weight of PVB and 55-45% by weight of the alloying copolymer(s).
  • a formulation may comprise 50% by weight of PVB and 50% by weight of the alloying copolymer(s).
  • This balanced weight ratio of the plasticizer composition relative to the construction polymer leads to an extrudable compound material to be used as part of a construction polymer blend in an amount of 10-75% by weight of the total polymer blend with typical optimal composition having around 40% by weight of plasticizer composition to around 60% by weight of construction polymer(s).
  • This method can also be used by directly mixing the individual components PVB and the alloying copolymer into the construction polymer or polymers.
  • PVB polyvinylbutyral
  • automotive front windows are claimed and thoroughly cleaned, sorted and reprocessed to the highest standards.
  • Pellets modified to be compatible with PVC are carefully compounded and extruded as a masterbatch to be blended directly in the PVC-extruding stream.
  • the confined formulation window ascertains the formation of the microstructures of the blend giving the desired modification of the product and the desired sterically lock of the plasticizer preventing migration, elution or solution of this.
  • the compound is primarily intended as a totally non-migrating plasticizer for flexible PVC applications and for impact modification of other polymers.
  • Composites and construction polymers can also benefit from this polymer-alloy with both elastic and acoustical properties.
  • Polymer type Modified Polyvinylbutyral-alloy in fixed stoichiometric ratio to Ethylene vinyl alcohol Copolymer Resins and/or other alloying copolymers. Due to the alloying of different polymer groups the resulting properties are not linear-combinations of known properties for the pure components, as also the inner microscopical structure are not just a blend of ordinary polymers.
  • PVB acts as a totally nonmigrating plasticizer for PVC and adds valuable properties to the PVC. Further the compound modifies recycled PVC as well, giving possibility to scale and tune properties of rPVC (recycled or reclaimed PVC) for extended and meaningful reuse. In this exists the option to extract unwanted plasticizers from the PVC by liquid CO 2 wash in commercially available washing machines, hereby giving possibility of recycling of PVC with a controlled macromolecular plasticizer being an alloyed copolymer.
  • PVB is used alone with PVC, there is poor compatibility between both, leading to limited plasticisation effect and brittleness of the resulting polymer. A less successful microstructure may also form giving unwanted drawbacks.
  • Embodiments of the method gives new design possibilities for PVC, since plasticization is scalable, and the microstructure of the blend reproducible and homogeneous.
  • Halogen free, phthalate free compounded alloy specialized to be a modern non-migrating PVC plasticizer with no toxicity and a green profile.
  • additives such as colorants, preservatives, stabilizers, and/or or antioxidants may be added to the polymer blend.
  • One or more suitable additives may be added in an amount of 0.01-65% by weight relative to the total polymer blend).
  • Suitable stabilizers for plasticized PVC based polymer blends according to the pre-sent invention are e.g. Calcium-Zinc complexes, stabilisers based on erythritols, e.g. pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate) (marketed as IrganoxTM 1010), phosphites, such as Tris(2,4-ditert-butylphenyl)phosphite (marketed as IrgafosTM 168), and/or mixtures thereof.
  • erythritols e.g. pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate) (marketed as IrganoxTM 1010)
  • phosphites such as Tris(2,4-ditert-buty
  • PVC stabilizers may be added in an amount of e.g. 1% calcium-zinc complex (markted as BaeropanTM MC 8850) and /or 0.4% pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (marketed as IrganoxTM 1010) and/or 0.2% Tris(2,4-ditert-butylphenyl)phosphite (marketed as IrgafosTM 168).
  • calcium-zinc complex labelted as BaeropanTM MC 8850
  • IrganoxTM 1010 Tris(2,4-ditert-butylphenyl)phosphite
  • Suitable colorants are among others Titanium (IV)-oxide, carbon black, masterbatch and ultrabatch compounded colorants. Also, fillers such as calciumcarbonate, fibers of natural or mineral origin and foaming agents like Hydrocerol® (made by Clairant) can be used.
  • Antioxidants have been added to all compositions (1 Baeropan MC 8850 for PVC and 0.4%
  • Plates have been produced on a Collin press at 180° C. and 150 bars for 3 minutes and then at 50° C. during 5 minutes for cooling.
  • plasticizer composition with 50%/50% by weight of PVB and an Ethylene Copolymer Resin (Elvaloy 741TM, produced by DuPont)
  • Plates have been produced on a Collin press at 180° C. and 150 bars for 3 minutes and then at 50° C. for 5 minutes for cooling. From these plates there has been prepared test samples according to the measures in the ISO and ASTM standards. The test specimens were cut from the plate in the required sizes described in the tests.
  • Antioxidants have been added to all compositions (1% PVC stabilizer as a Calcium-zinc complex (BaeropanTM MC 8850) and 0.4% PVB stabilizer Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (IrganoxTM 1010)+0.2% Tris(2,4-ditert-butylphenyl)phosphite (IrgafosTM 168)
  • Test specimens according to the present invention were prepared from a plasticizer blend of 50% by weight of PVB with 50% by weight of Ethylene Copolymer Resin (ElvaloyTM 741) plasticizer composition (named PVB compound in FIGS. 1-17 ) added in an amount of 40% by weight to 60% by weight of PVC:
  • ISO 178:2010 shows a decrease relative to the PVC of ⁇ 85% on reference specimens as well as test specimens made according to example 1. Results.
  • Measurements have been done by testing specimens of rectangular cross-section being 80 ⁇ 10 ⁇ 4 mm, resting on two supports, being deflected by a loading edge acting on the specimen midway between the supports.
  • the test specimen is deflected in this way at a constant rate at midspan until rupture occurs at the outer surface of the specimen or until a maximum strain of 5% is reached, whichever occurs first.
  • the force applied to the specimen and the resulting deflection of the specimen at midspan are measured.
  • the resulting softening/plasticization is interpreted as an evidence of the claimed function of the compound.
  • FIG. 1 where the average values of flexural modulus is shown for the pure PVC reference specimen and the test specimen made with a plasticizer blend of PVB+Elvaloy 741 as explained above.
  • Tensile modulus measured according to ISO 527-2:2012 shows a decrease relative to pure PVC. Measurements have been done using an extensometer measuring specimens 20 mm in the parallel parts and with an overall length of 35 mm. Thickness is 1 mm. The type of the specimens is referred to as 5 A.
  • the plasticizing of PVC by the plasticizer composition according to the present invention and as discussed in example 1 gives a change of ⁇ 83%, see FIG. 2 .
  • Elongation at break measured according to ISO 527-2:2012 shows an increase relative to PVC of 89%, see FIG. 4 .
  • Measurements have been done using an extensometer measuring specimens 20 mm in the parallel parts and with an overall length of 35 mm. Thickness is 1 mm. The type of the specimens is referred to as 5 A in the standard.
  • the increased ability to stretch is interpreted as an effect of the plasticization effect of the compound.
  • Tensile strength shows relative to PVC a change of ⁇ 66% see FIG. 5 . Measurements have been done using an extensometer measuring specimens 20 mm in the parallel parts and with an overall length of 35 mm. Thickness is 1 mm. The type of the specimens is referred to as 5 A.
  • the change in tensile strength is interpreted as an effect of the plasticization effect of the compound.
  • a PVC reference specimen is compared to test specimens of polymer blends with 40% rPVB, and to the plasticizer according to the present invention being 50%/50% blend rPVB/Elvaloy 741 (called 1:1 on FIG. 6 ), and a compound being 75%/25% blend rPVB/Elvaloy 741 (called 3:1 on FIG. 6 ). (the prefix “r” means that the relevant polymers are recycled from waste fractions of that specific polymer.)
  • Flexural modulus measured according to ISO 178:2010 shows a decrease relative to the PVC reference specimen, see FIG. 6 .
  • Measurements have been done by testing specimens of rectangular cross-section being 80 ⁇ 10 ⁇ 4 mm, resting on two supports, being deflected by a loading edge acting on the specimen midway between the supports.
  • the test specimen is deflected in this way at a constant rate at midspan until rupture occurs at the outer surface of the specimen or until a maximum strain of 5% is reached, whichever occurs first.
  • the force applied to the specimen and the resulting deflection of the specimen at midspan are measured.
  • Tensile modulus is tested on specimens with a composition as described in example 7.
  • Tensile modulus measured according to ISO 527-2:2012 shows a decrease relative to PVC, see FIG. 7 . Measurements have been done using an extensometer measuring specimens 20 mm in the parallel parts and with an overall length of 35 mm. Thickness is 1 mm. The type of the specimens is referred to as 5 A in the standard.
  • the plasticizing of PVC by the compound claimed shows that PVC+40% compound in a 1:1 ratio of PVB and Elvaloy 741® shows a significantly lower flexural modulus than if a 3:1 mixing ratio was applied. A further increase like 1:2 will give higher tensile modulus.
  • Shore D hardness is tested on specimens with a composition as described in example 7.
  • Shore D hardness measured according to the specification in ASTM D2240-15e1 using a Reichert MHP microhardness tester with a Vickers diamond shows decrease in hardness, depending on the amount of compound used, see FIG. 8 .
  • Elongation at break is tested on specimens with a composition as described in example 7.
  • Elongation of break measured according to ISO 527-2:2012 shows an increase relative to PVC. Measurements have been done using an extensometer measuring specimens 20 mm in the parallel parts and with an overall length of 35 mm. Thickness is 1 mm. The type of the specimens is referred to as 5 A.
  • the plasticizing of PVC by the plasticizer composition according to embodiments of the present invention shows that PVC+40% compound in a 1:1 ratio shows a significantly higher elongation at break than if a 3:1 mixing ratio was applied.
  • PVB alone with PVC makes a very inelastic product, and the results shows that a certain optimum exists were the values change rapidly, see FIG. 9 .
  • ISO 527-2:2012 shows a decrease relative to PVC. Measurements have been done using an extensometer measuring specimens 20 mm in the parallel parts and with an overall length of 35 mm. Thickness is 1 mm. The type of the specimens is referred to as 5 A.
  • the plasticizing of PVC by the compound claimed shows that PVC+40% compound in a 1:1 ratio shows a significantly lower tensile strength than if a 3:1 mixing ratio was applied, see FIG. 10 . A further increase like 1:2 will give higher tensile strength.
  • Charpy strength is tested on specimens with a composition as described in example 7.
  • Charpy strength is tested according to ISO 148-1:2016 of specimen 55 ⁇ 10 ⁇ 10 mm.
  • This test consists of breaking a notched test piece with a single blow from a swinging pendulum.
  • the notch in the test piece has a specified geometry and is in the middle between two supports, opposite to the location which is impacted.
  • the energy absorbed in the sample is graphed.
  • Thee result shows a better energy absorption due to energy dissipation in the modified compound, mainly from the PVB molecular backbone, see FIG. 11 .
  • Charpy strength is tested on reference specimens of pure PVC and test specimens with a composition of
  • Increase of contact angle to water is measured as in ISO 15989:2004.
  • Droplets of double quarts redistilled water is applied with a manual micro syringe equipped with a platinum flat tip needle on top of the specimen.
  • Photographs in 1:1 with LED illumination are image analysed in ImageJ (NIST) making both elliptical and spherical approximation to the drop surface with compensation for gravity.
  • the contact angle is determined on both sides of the image and mediated.

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DKPA201870168 2018-03-15
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EP18200170.1 2018-10-12
EP18200170 2018-10-12
EP18200170.1A EP3540009A1 (fr) 2018-03-15 2018-10-12 Modification de polymères de construction recyclés et/ou vierges, à l'aide de poly vinyl butyral (pvb) ou de pvb recyclé à partir de flux de déchets industriels et copolymère d'alliage
PCT/DK2019/050094 WO2019174700A1 (fr) 2018-03-15 2019-03-15 Modification de polymères de construction vierges et/ou recyclés en utilisant du polybutyral de vinyle (pvb) ou du pvb recyclé à partir de flux de déchets industriels et un copolymère d'alliage

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WO1993002141A1 (fr) 1991-07-23 1993-02-04 E.I. Du Pont De Nemours And Company Recyclage de polybutyral de vinyle
US5514752A (en) * 1993-09-22 1996-05-07 Hoechst Aktiengesellschaft Polypropylene molding composition having improved surface properties
US5770654A (en) 1993-10-13 1998-06-23 E. I. Du Pont De Nemours And Company Polyamide compositions toughened with waste plasticized polyvinylbutyral
WO1999057196A1 (fr) 1998-05-06 1999-11-11 E.I. Du Pont De Nemours And Company Melanges polymeres de polyvinylbutyral avec du chlorure de polyvinyle
WO2018041007A1 (fr) 2016-08-30 2018-03-08 南通万德科技有限公司 Matériau macromoléculaire et matériau composite métallique et leur procédé de préparation

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WO1993002141A1 (fr) 1991-07-23 1993-02-04 E.I. Du Pont De Nemours And Company Recyclage de polybutyral de vinyle
US5514752A (en) * 1993-09-22 1996-05-07 Hoechst Aktiengesellschaft Polypropylene molding composition having improved surface properties
US5770654A (en) 1993-10-13 1998-06-23 E. I. Du Pont De Nemours And Company Polyamide compositions toughened with waste plasticized polyvinylbutyral
WO1999057196A1 (fr) 1998-05-06 1999-11-11 E.I. Du Pont De Nemours And Company Melanges polymeres de polyvinylbutyral avec du chlorure de polyvinyle
US6506835B1 (en) * 1998-05-06 2003-01-14 E. I. Du Pont De Nemours And Company Polymer blends of polyvinyl butyral
WO2018041007A1 (fr) 2016-08-30 2018-03-08 南通万德科技有限公司 Matériau macromoléculaire et matériau composite métallique et leur procédé de préparation

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